Erosion-corrosion resistant aluminum radiator clad tubing

ABSTRACT

A composite aluminum article having increased resistance to erosion corrosion in aqueous environments comprising an aluminum base alloy cladding consisting essentially of 0.8 to 1.3 percent zinc, 0.7 percent maximum silicon plus iron, 0.10 percent maximum copper, 0.10 percent maximum manganese, 0.10 percent maximum magnesium, balance essentially aluminum, bonded to at least one side of an aluminum base alloy core consisting essentially of manganese from 1.0 to 1.5 percent, chromium from 0.1 to 0.4 percent, copper from 0.05 to 0.4 percent, balance essentially aluminum.

United States Patent" [191 Anthony et al.

11] 3,809,155 [451 May 7,1974

[ EROSION-CORROSION RESISTANT ALUMINUM RADIATOR CLAD TUBING Inventors: William H. Anthony; James M.

Popplewell, both of Guilford, Conn.

Assignee: Olin Corporation, New Haven, Conn.

Filed: Feb. 2, 1972 Appl. No.: 222,795

US. Cl 165/133, 138/38, 165/172 Int. Cl. F28f 13/18 Field of Search....; 165/180, 152, 133, 172;

[56] References Cited UNITED STATES PATENTS 3,530,932 9/1970 Pryor 165/180 Primary Examiner-Charles Sukalo Attorney, Agent, or Firm-Robert H. Bachman [5 7] ABSTRACT A composite aluminum article having increased resistance to erosion corrosion in aqueous environments comprising an aluminum base alloy cladding consisting essentially of 0.8 to 1.3 percent zinc, 0.7 percent maximum silicon plus iron, 0.10 percent maximum copper, 0.10 percent maximum manganese, 0.10 percent maximum magnesium, balance essentially aluminum, bonded to at least oneside of an aluminum base alloy core consisting essentially of manganese from 1.0 to 1.5 percent, chromium from 0.1 to 0.4 percent,

copper from 0.05 to 0.4 percent, balance essentially aluminum. 7

6 Claims, 2 Drawing Figures BACKGROUND OF THE INVENTION It is highly desirable to develop composite aluminum articles having improved resistance to erosion corrosion in aqueous environments due to the wide use of aluminum commercially in aqueous environments.

For example, aluminum tubing which is used in heat exchangers such as aluminum radiators shouldhave high resistance to erosion corrosion damage by the aqueous heat exchangefiuid.

Aluminum automobile radiators have been extensively tested. Unfortunately, however, materials which are suitable are often subject to erosion corrosion damage and, hence, have a limited life expectancy due to the development of'leaks in service. The leaksmay be developed due to the erosion corrosion channeling excavating the tube wall as the coolant stream passes around blockages in the tubes. Very high stream velocities which would occur in such channels can readily result in erosion corrosion damage unless the material is highly resistant to this type of damage.

Accordingly, it is an object of the present invention to provide composite aluminum articles having improved resistance to erosion corrosion in aqueous environments.

It is a further object of the present invention to provide composite aluminum tubing having improved resistance to erosion corrosion in aqueous environments.

It is a still further object of the present invention to provide an improved heat exchange assembly utilizing said tubing, a process for improving heat transfer with resistance to erosion corrosion in an aqueous environment and an improved heat transfer system.

Further objects and advantagesof the present invention will appear from the ensuing specification.

SUMMARY OF THE INVENTION In accordance with the present invention it has now been found that the foregoing objects and advantages may be readily achieved.

Composite aluminum articles of the present invention have substantially improved resistance to erosion core consisting essentially of manganese from 1.0 to

1.5 percent, chromium from 0.1 to 0.4 percent, copper from 0.05 to 0.4 percent, and the balance essentially aluminum.

The present invention also contemplates a composite aluminum tubing and a highstrength heat exchange assembly having improved resistance to erosion corrosion in an aqueous environment. The assembly comprises at least one header connected by at least one tube and a secondary heat exchange surface connected to said tube; The tube is the improved composite aluminum tubing of the present invention. The preferred embodiment includes two parallel headers connected by a plurality of said tubes perpendicular therewith, with corrugated fin stockmaterial being bonded to said tubes. v

The present invention also contemplates an improved heat transfer system and a process for providing heat transfer with resistance to erosion corrosion in an aqueous environment. The process comprises provid-. ing the metal tubing of the present. invention having entrance and exits ends, affixing said entrance and exit ends to two tube sheets, passing a first aqueous liquid through said tubing and contacting the external surface of the tubing with a second fluid in heat exchange relationship with the first fluid.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. I is a perspective ent invention.

FIG. II is a front view, with portions cutaway, of an automobile radiator including the tubing of the present invention.

view, of the tubing of the pres- DETAILED DESCRIPTION to 1.5 percent, chromium from 0.1 to 0.4 percent, cop-' per from 0.05to 0.4 percent, and the balance essentially aluminum. I

As indicated hereinabove, the present invention is characterized by surprising resistance to erosion corrosion in an aqueous environment wherein the aluminum alloy cladding is exposed to the aqueous environment. It has also been found that this improved resistance can be accomplished with retention of excellent physical properties.

In addition to the foregoing, the composite of the present invention has improved resistance to pitting corrosion.

The excellent erosion corrosion resistance of the composite of the present invention is highly desirable commercially. This property admirably lends the tubing of the present invention to use in heat exchange assembly such as in an aluminum radiator and the tubing of the present invention would result in a substantially longer useful life. The surprising properties achieved in accordance with the present invention would give the material of the present invention good utility in other applications using high speed fluids.

It has been found that in aqueous environments wherein erosion corrosion or impingment attack oc curs, as for example, upon the inside wall or cladding. 2, as shown in FIG. I of the tubing carrying the aqueous solution, that the aluminum composite of the present invention has surprising resistance: to this destructive attack. This resistance is obtained since, should perforation of the aluminum alloy cladding 2, as shown in FIG. I, occur, further localizedcorrosion is retarded or ding occur, as'in impingement attack, the current generated by the relatively large anode and small cathode is such as to effectively inhibit penetration of the core and hence the core is cathodically protected from further attack.

The cladding material of the present invention may also contain impurities such as up to 0.7 percent silicon plus iron, up to 0.1 percent copper, up to 0.1 percent manganese, up to 0.1 percent magnesium, others 0.05 percent each, total 0.15 percent.

The core material of the present invention may also contain impurities such as up to 0.6 percent silicon, up to 0.7 percent iron, up to 0.1 percent zinc and others 0.05 percent each, total 0.15 percent.

Naturally the cladding may be bonded to the outside surface of the core should the aqueous media flow around the tubes rather than through them or the core may advantageously be clad on both sides wherein a first aqueous medium passes through the tubing and a second aqueous medium passes around the tubing.

The tubing of the present invention normally, but not necessarily has a wall thickness no larger than 0.10 inch. When the tubing of the present invention is used in a high strength aluminum radiator, the tubing has a wall thickness 0.030 inch or smaller and perferably has a wall thickness from 0.010 to 0.020 inch. For heat exchange applications in general, the tubing of the present invention most advantageously has a wall thickness of 0.1 inch and smaller.

The percentage thickness of the cladding of the tubing of the present invention is not critical but generally ranges from 5 to 25 percent of the total composite wall thickness of the composite in order to insure a sufficient thickness of the core material for strength as well as sufficient thickness of the cladding in order to provide for a sufficiently long cladding life in service.

The tubing of the present invention may be readily prepared by conventional methods. For example, aluminum ingots may be conventionally prepared and rolled to strip in a conventional manner and then strips of the clad and core material rolled together. The material may then be welded .or extruded into tubing having the desired configuration. The tubing may also be formed by drawing of the core in tubular form over the cladding material in tubular form if desired.

If desired fins of an alloy such as the AA 4XXX series or of the core material may be provided on an exposed surface of the core material and bonded thereto by, for

example a brazing filler metalor by providing an additional cladding bonded to the core which is suitble for bonding to the tin material, such as an AA 4XXX series alloy.

Radiator tubing is generally seam welded into substantially round tubing and flattened into an oval or fiat cross section. Thus, bonding together of the clad and core material may be readily achieved by rolling of the composites together before welding. The smaller dimension is preferably from 0.05 to 0.2 inch. The larger dimension ispreferably from 0.3 to 1.2 inch. For heat exchange applications in general, the tubing of the present invention may be advantageously used having an outside diameter (O.D.) up to several inches and preferably from V4 inch CD. to 2 inches OD.

The aluminum radiator may be prepared in a conventional manner utilizing brazing in a continuous aluminum radiator manufacturing line. As a specific example, an aluminum radiator may be prepared from tubing of the present invention having a 17 mil thick wall and fin stock which may be either the same alloy as, the core material or a conventional aluminum alloy of the 4XXX series for example, aluminum alloy 4043, 4343 or 4045. An assembly is prepared having the configuration of the desired aluminum radiator. The fixtured assembly is dip coated with a salt flux and then furnace brazed in a continuous manner ona production line.

The radiators pass through an air furnace where the brazing filler metal melts and then solidifies resulting in the formation of a rigid assembly. Alternatively, fluxless brazing procedures may be used.

As aforementioned an additional cladding of a brazing alloy such as an AA 4XXX series alloy may be bonded to the exposed surface of the core material for bonding to the fin stock, if desired.

Thus, in accordance with the present invention the high strength heat exchange assembly may have the configuration shown in FIG. I], which represents an illustrative heat exchanger embodiment. Referring now to FIG. II, the radiator assembly includes a heat dissipating unit or core 6 having at opposite ends a top tank or inlet header 8 and a bottom tank or outlet header 10, adapted for connection, respectively, with. the discharge and intake conduits or a cylinder block cooling jacket for the flow of cooling aqueous medium from one tank to the other. The core 6 is made up of a number of fluid passageways of water tubes 12 of the present invention. The tubes are spaced apart by fin strips 14. The fins are folded or corrugated between tubes 12 and extend between adjacent walls or adjoining tubes to divide the space into a number of relatively small air cells 16.

The present invention will be more readily apparent from a consideration of the following illustrative examples.

EXAMPLE I Three alloys, Alloys A, B and C, were Durville cast and then homogenized at l,125F for about 8 hours and air cooled. The composition of the resulting alloys is shownin Table I below:

Percent composition lngots A and B of Example I were scapled to 1.5 inch and then wire brushed and vapor degreased. lngot C was hot rolled at 800 to 0.25 inch gage using a 0.1 inch pass with reheating to 800F with each second pass. The hot rolled material was then cold rolled to 0.050 inch gage. The 0.050 inch gage material of ingot C was then welded to each of the A and B ingot slabs on four sides to form A and B composites respectively leaving 1 inch long openings in the weld across one of the shorter edges so that air could be expelled during further rolling of the composites. The composites were then heated to 800F for 5 minutes and given skin passes of about a 3 percent reduction each with the partially opened edge facing in a direction opposite to the travel of the composites. The composites were then reheated to 800F, hot rolled to 0.25 inch gage, and then cold rolled to 0.050 inch gage.

Thecladding thickness of the A and B composites were then measured on mounted and polished sections and found to be 1.5 and 1.6 mils thick respectively.

The composites of Example 1 were then heated up and cooled down using a pit furnace in such a way to simulate the effect of a brazing step in a continuous aluminum radiator manufacturing line. This was done in order to allow for any possibleinterdiffusion effects which could result in reducing the electrode potential difference between the components of each composite during the aluminum radiator manufacturing. The heat up and cool down cycle is as follows: The composites were heated to 1,150F and cooled to 800F within two minutes at a constant cooling rate and then quenched in water at 160F.

EXAMPLE Ill The composites of Example land 11 were cut into appropriate size specimens and subjected to impingement by a plurality of jets of an aqueous antifreeze material simulating the effects of long term erosion corrosion in automobile radiators. Uncomposited Alloy A, further rolled to 0.050 inch after processing to 1.5 inch thick ness in Example I, and the composite A were employed as controls. The antifreeze material was a commercial, inhibited aqueous ethylene glycol containing a 45 percent nominal by volume ethylene glycol which wasdirected onto the samples at a temperature of about 200F with the velocity of the jets at about 98 feet per second. The test was carried out for 6 days.

At the end of the test the specimens were removed and rinsed in distilled water followed by solvent rinses in methanol and benzene. The samples were then chemically cleaned by immersing them in an aqueous bath of chromic plus phosphoric acids at 80C. They were then rinsed in distilled water, dried and the depths of the resultant impingement craters measured. The depth of attack in the control composite comprising the A plus C material or composite A and the uncomposited alloy A material was found to be about three mils whereas the depth of attack in the composite comprising the B and C material or composite B was found to be about 1.8 mils maximum. The exposed core of the B composite or the B alloy was found to be substantially free of attack attesting to the galvanic protection afforded to the B alloy by the C alloy cladding of the composite whereas the exposed core material of the A composite or the A alloy had numerous small pits indicating that the galvanic protection afforded to the alloy by the C alloy cladding is practically nonexistant.

The cladding adjacent to the exposed core of the B composite was found to be substantially consumed therebyindicating cathodic protection was provided to the B alloy core whereas there was substantially less consumption of the cladding in the crater rim of the control A composite.

EXAMPLE IV The present example illustrates the potential difference between the alloys of the composite of the present invention.

Specimens were cut from the A and B'alloys and from 0.050 inch gage C cladding material of Example I for impingement testing as in Example III. A portion of each specimen was passed through a special composite gasket of silicon rubber in the jet chamber of the jet tester without making electrical contact with the flange or leaking any antifreeze when the gasket was tightened. Special rubber inserts were employed so that the specimens were mounted without incurring any electrical leakage to the stainless-steel jet tester chamber. In this manner it was possible to mount dissimilar specimens in jet testchambers and measure the current flow between them while they were subjected to antifreeze jet impingement at any temperature desired.

The current flow was measured by monitoring the potential drop across a 2 ohm resistor which shunted the electrodes externally. The value of the resistor was less than 0.5 percent of the total electrolytic resistance path in the antifreeze between the two test specimens. In this manner the current flow between Alloy C of Example and Alloy A of the present example and Alloy C of Example 1 and Alloy B of the present example was monitored while the antifreeze impinged on the samples at 98 feet per second. The temperature was cycled up and down from 40 to 105C for three successive cycles. The direction of current flow throughout the cycling was such that the alloy C of Example 1 component remained anodic for both couples.

It was apparent that throughout the several cycles the current output of the Alloy B-Alloy C was about 5 times as great as the Alloy A-Alloy C. Thus a startling and unexpectedly large difference to the protective cathodic current is provided by the .Alloy C anode materal coupled to Alloy B and this is epecially true within the temperature range of to 105C where automobiles normally operate. In particular the Alloy A-Alloy C couple provided 16 microamps current in the descending leg of the third cycle at a temperature of 933C (or 200F) while the Alloy BAlloy C couple provided microampsat the same point.

This invention may be embodied in other forms or carried out in other ways without departing from the spirit or essential characteristics thereof. The present embodiment is therefore to be considered as in all respects illustrative and not restrictive, the scope of the invention being indicated by .the appended claims, and all changes which come within the meaning and range of equivalency are intended to be embraced therein.

What is claimed is:

1. A composite metal tubing having improved resistance to erosion corrosion in an aqueous environment comprising an aluminum base alloy cladding consisting of 0.8 to 1.3 percent zinc, 0.7 percent maximum silicon plus iron, 0.10 percent maximumcopper, 0.10 percent maximum manganese, 0.10 percent maximum magneslum, balance essentially aluminum, bonded to at least one side of an aluminum base alloy core consisting of manganese from 1.0 to 1.5 percent, chromium from 0.1 to 0.4 percent, copper from 0.05 to (0.4 percent balance essentially aluminum.

' 8 each, total 0.15 percent.

5. A tubing according'to claim 1 having a wall thickness from 0.010 to 0.030 inch.

6. A tubing according to claim 1 wherein said cladding is bonded to one side of said core and further having a brazing layer of a material selected from the group consisting of the AA 4XXX series alloys bonded to the opposing side of said core. 

2. A tubing according to claim 1 wherein said cladding is bonded to opposing surfaces of said core.
 3. A tubing according to claim 1 wherein said cladding contains up to 0.7 percent silicon plus iron, up to 0.1 percent copper, up to 0.1 percent manganese, up to 0.1 percent magnesium and others 0.05 percent each, total 0.15 percent.
 4. A tubing according to claim 1 wherein said core contains up to 0.6 percent silicon, up to 0.7 percent iron, up to 0.1 percent zinc, and others 0.05 percent each, total 0.15 percent.
 5. A tubing according to claim 1 having a wall thickness from 0.010 to 0.030 inch.
 6. A tubing according to claim 1 wherein said cladding is bonded to one side of said core and further having a brazing layer of a material selected from the group consisting of the AA 4XXX series alloys bonded to the opposing side of said core. 